EP1825553B1 - Electrically conductive fuel cell contact materials - Google Patents
Electrically conductive fuel cell contact materials Download PDFInfo
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- EP1825553B1 EP1825553B1 EP05803472.9A EP05803472A EP1825553B1 EP 1825553 B1 EP1825553 B1 EP 1825553B1 EP 05803472 A EP05803472 A EP 05803472A EP 1825553 B1 EP1825553 B1 EP 1825553B1
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- fuel cell
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- 239000000463 material Substances 0.000 title claims description 65
- 239000000446 fuel Substances 0.000 title claims description 47
- 239000002245 particle Substances 0.000 claims description 54
- 239000011148 porous material Substances 0.000 claims description 38
- 239000011362 coarse particle Substances 0.000 claims description 21
- 239000010419 fine particle Substances 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 11
- 229910010293 ceramic material Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 5
- 230000001351 cycling effect Effects 0.000 claims description 2
- 230000035882 stress Effects 0.000 description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000005245 sintering Methods 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000005382 thermal cycling Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- -1 oxygen ions Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- VMTPSMDWKJCNNA-UHFFFAOYSA-N cobalt lanthanum oxonickel Chemical compound [Ni]=O.[Co].[La] VMTPSMDWKJCNNA-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002204 La0.8Sr0.2MnO3 Inorganic materials 0.000 description 1
- 229910002254 LaCoO3 Inorganic materials 0.000 description 1
- 229910015468 Ni1-xCox Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- FVROQKXVYSIMQV-UHFFFAOYSA-N [Sr+2].[La+3].[O-][Mn]([O-])=O Chemical compound [Sr+2].[La+3].[O-][Mn]([O-])=O FVROQKXVYSIMQV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910052963 cobaltite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0215—Glass; Ceramic materials
- H01M8/0217—Complex oxides, optionally doped, of the type AMO3, A being an alkaline earth metal or rare earth metal and M being a metal, e.g. perovskites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/43—Electric condenser making
Definitions
- the present invention relates to a multilayer design of contact materials which may include electrically conductive perovskites.
- High temperature fuel cells like solid oxide fuel cells comprise an electrolyte sandwiched between a cathode and an anode.
- Oxygen combines with electrons at the cathode to form oxygen ions, which are conducted through the ion-conducting ceramic electrolyte to the anode.
- oxygen ions combine with hydrogen and carbon monoxide to form water and carbon dioxide thereby liberating electrons.
- the fuel cells are stacked and interleaved with interconnect plates which distribute gases to the electrode surfaces and which act as current collectors.
- Contact pastes are used to bond the electrode to an interconnect and must therefore be electrically conductive.
- U.S. Patent No. 6,420,064 a cathode contact layer comprised of lanthanum cobaltate is disclosed.
- German Patent No. DE 19627504 discloses a connection lead plate for a high temperature fuel stack having at least part of its surface coated with a contact layer comprising a lower oxidic layer, a middle ceramic layer, and an upper ceramic layer having less porosity than the upper ceramic layer.
- Lanthanum cobaltate also known as lanthanum cobaltite, is a perovskite, which is a well-known class of mineral oxides characterized by a cubic or orthorhombic crystalline structure.
- Perovskites may be described by the formula ABO 3 , where A represents divalent and/or trivalent ions and B represents trivalent and/or tetravalent ions, while the O atom is the oxygen ion.
- the divalent, trivalent and tetravalent ions may include La 3+ , Sm 3+ , Sr 2+ , Ca 2+ , Co 3+ , Ni 3+ , ,Fe 3+ , Cr 3+ , Mn 3+ or Mn 4+ amongst others.
- this ABO 3 structure in a general sense can be thought of as face centered cubic (FCC) lattice with A atoms at the corners and the O atoms on the faces.
- the B atom is located at the center of the lattice.
- LC Some perovskites such as LC are reasonably good electrical conductors.
- LC suffers from one significant disadvantage. If sintered, its coefficient of thermal expansion is significantly greater than that of the bulk cell. Consequently, thermal cycling of the fuel cell results in large thermal stresses and the contact paste may break away from the cell and interconnect resulting in poor electrical contact.
- contact paste materials which display better interface performance with the cell can have poor interface performance with the interconnect.
- the present invention provides for a contact material comprising stress relief means for use in fuel cell stack between a fuel cell electrode and an interconnect.
- the contact material is electrically conductive and porous to permit the flow of reactant to the electrode.
- the electrode is a cathode.
- the invention comprises a fuel cell stack comprising:
- the stress relief layer may additionally comprise a separately formed layer of a conductive ceramic material which is pressed against the pore forming material. That separately formed layer may itself include particles of a pore forming material.
- the pore forming material combusts, leaving a void space. If the pore forming material was introduced in particular form, the stress relief layer will be more porous and structurally weaker. If the pore forming material was introduced in a layer, a fracture plane will be left. Alternatively, a fracture plane may be introduced by forming two halves of a stress relief layer and contacting them without binding or otherwise linking them together.
- the invention may comprise a method of forming a stress relief layer in a contact layer disposed between at least one electrode of a fuel cell and an adjacent interconnect, the contact layer comprising at least two outer layers and a central layer of electrically conductive material, wherein one of the outer layers adheres to the at least one electrode and the other outer layer adheres to the interconnect, wherein the central layer comprises the stress relief layer, said method comprising the steps of: forming the stress relief layer from:
- the present invention provides for a perovskite contact material which may be used to interface between a solid oxide fuel cell electrode and an interconnect or a current collector.
- a perovskite contact material which may be used to interface between a solid oxide fuel cell electrode and an interconnect or a current collector.
- a portion of a fuel cell stack is illustrated as an exploded view in Figure 1 and in cross-section in Figure 2 .
- a single fuel cell (10) consists of an anode (12) supported structure having a thin electrolyte (14) and cathode (16) layer.
- a single fuel cell unit also includes an interconnect (18) which may be a monolithic plate having flow-directing ribs (20) stamped as shown in Figure 1 .
- the ribs (20) assist in providing an even distribution of air flow across the entire surface of the cathode between the air intake and exhaust manifolds.
- the cathode may comprise a composite material comprising a noble metal such as palladium and a ceramic such as yttrium stabilized zirconium, as described in co-owned U.S. Patent No. 6,420 ,064 .
- the contact material (22) of the present invention is applied to one or both of the cathode and interconnect faces upon assembly of the fuel cell stack.
- the contact material may be applied by screen printing, as is well known in the art.
- a layer may be screen printed onto the cathode surface and allowed to dry.
- the contact material paste dries as a porous green ceramic layer and may then be sintered prior to assembly of fuel cell units in the stack. Alternatively, the material may not be sintered before stack assembly, in which case, the contact material is sintered during operation of the fuel cell.
- a second contact layer is then applied (the fracture layer) and dried.
- a thin layer of the contact material as a wet paste is screen printed onto the cell dried layer(s) or the interconnect surface and the interconnect is then contacted with the cathode surface. If the interconnect is corrugated or ribbed, the contact material may or may not fill in the void areas of the interconnect. The contact material must be porous to allow reactants to flow from the interconnect and reach the fuel cell electrode.
- Perovskites of the present invention may be described by the general formula ABO 3 , where A is a doped or undoped rare earth metal, lanthanide or mixed lanthanide, and B is a doped or undoped transition metal, where the perovskite has a coefficient of thermal expansion (CTE) which closely matches that of the fuel cell electrode or the interconnect.
- CTE coefficient of thermal expansion
- a CTE is considered to closely match another CTE if it is within about 5 x 10 -6 K -1 of the other CTE.
- the coefficient of thermal expansion of a material may be determined empirically or by estimation using known and published values. Whether or not two materials have closely matched coefficients of expansion may also be determined experimentally by thermal cycling the two materials adhered to each other and observing the loss of adhesion.
- a contact material of the present invention may be applied to an interconnect or to a fuel cell electrode, and the two materials thermally cycled within the operating temperature range of a solid oxide fuel cell. If no, or substantially none, loss of adhesion is observed, then a person skilled in the art may conclude that the CTE's of the two materials are likely to be closely matched.
- the transition metal may comprise cobalt, nickel, iron, copper, zinc or lead.
- B comprises cobalt doped with nickel as follows: Co 1-y Ni y where 0.3 ⁇ y ⁇ 0.7.
- y is about 0.4.
- Nickel is a preferred material because the inclusion of nickel in the B-site tends to lower the coefficient of thermal expansion.
- the perovskite formed with nickel is highly electrically conductive but is not very reactive with other materials.
- the A element is preferably lanthanum and may be doped with an alkaline earth metal such as strontium, barium or calcium to improve electrical conductivity. Therefore, A may comprise La 1-x E x wherein E is an alkaline earth metal and 0.0 ⁇ x ⁇ 0.8. Lanthanum cobalt nickel oxide materials are referred to herein as "LCN".
- a particularly preferred LCN material is La 1-x E x Co 0.6 Ni 0.4 where x is greater than or equal to zero and less than about 0.7. Preferably, x is less than 0.5.
- the A and B elements may be stoichiometric or non-stoichiometric. If non-stoichiometric, the A:B ratio may vary from about 0.9 to about 1.1.
- the perovskites of the present invention may be applied as a paste using well-known solvents and binders to either or both of the cathode and interconnect in a fuel cell unit and sintered prior to assembly of the fuel cell stack.
- the paste may be unsintered prior to assembly of the fuel cell stack and sintered in situ upon operation of the fuel cell stack.
- Stack operating temperatures may reach about 800° C.
- Sintering additives to lower the sintering temperature of the perovskite may be desirable or necessary. Suitable sintering additives or aids such as copper, silver, glass frit or tin are well-known in the art.
- a contact material of the present invention may also be used in the interface between the anode surface and an interconnect and its use is not restricted to the cathode surface.
- the contact paste material is applied in a multilayer configuration which may provide better resistance to thermal cycling degradation and long term degradation.
- the contact paste is applied in three layers in which the outer contact layers adhere to the fuel cell electrode and interconnect respectively, and the central layer comprises a stress relief layer.
- the outer contact layers comprise fine conductive particles while the stress relief layer comprises coarse conductive particles.
- the conductive particles in either or both the fine and coarse layers preferably comprise conductive perovskites, including those perovskites described herein, or perovskites having a K 2 NiF 4 -type structure (e.g. La 2 Ni 1-x Co x O 4 ) or any other electrically conducting ceramic powder compatible with the fuel cell electrolyte and electrode materials.
- fine particles comprise particles having diameters less than about 2 ⁇ m and preferably about 0.3 to about 1.1 ⁇ m.
- coarse particles comprises particles that are at least one and a half times the particle diameter of the fine particles, and preferably greater than about twice the diameter of the fine particles.
- coarse particles Preferably, coarse particles have diameters greater than about 1 ⁇ m and more preferably greater than about 1.5 ⁇ m.
- the stress relief layer may be formed of a conductive ceramic material, such as the perovskites described herein, which has similar chemistry and similar sintering characteristics to the fine outer layers, but which comprises coarse particles.
- the stress relief layer may be formed from a conductive ceramic material which has significantly different sintering characteristics than the fine layers.
- the stress relief layer may be formed of lanthanum strontium manganite (LSM), which has a significantly higher sintering temperature than LC or LCN.
- LSM lanthanum strontium manganite
- the stress relief particle size may be fine or coarse.
- the stress relief layer would not sinter or sinter to the same extent as the other layers.
- the stress relief layer may be formed of a porous metallic material such as expanded metal, or a fine metal mesh.
- the stress relief layer may be porous or highly porous.
- the stress relief layer comprises coarse particles and has a porosity of between about 25% to about 70%.
- the stress relief layer may be about 30% to about 50% porous.
- Porous metallic stress relief layers may be more porous, up to about 95%.
- the fine particle layers may be thinner or thicker than the coarse central layer.
- the fine particle layers are less than about 25 ⁇ m thick while the coarse central layer may be about 10 ⁇ m to about 50 ⁇ m thick.
- the combined thickness of the multilayer contact materials may be about 60 to 120 ⁇ m, depending on the stack design and seal thicknesses. The combined thickness should preferably not exceed 200 ⁇ m.
- the layers may be applied by screen printing a paste and sintered prior to stack assembly or left unsintered as described above.
- Sintering aids may be included if necessary or desired. The necessity or desirability of a sintering aid may be determined empirically by one skilled in the art.
- a layer of fine lanthanum cobalt nickel oxide (LCN) particles is applied to the fuel cell electrode surface by screen printing.
- the LCN particles have an average particle size of about 1.0 ⁇ m with about 50% of the particles falling in the range of about 0.5 ⁇ m to about 1.1 ⁇ m.
- This layer of fine LCN particles may be less than about 25 ⁇ m thick and may or may not be sintered.
- a layer of coarse LCN material is applied by screen printing onto the first fine layer and allowed to dry.
- the coarse LCN particles have an average particle size of between about 2 to about 3 ⁇ m, with a majority of the particles falling in the range between about 1 ⁇ m to about 10 ⁇ m.
- the remaining fine layer of LCN is screen printed onto this layer on the cell or the interconnect just prior to assembly of the stack.
- LC may be used in place of LCN in any or all of the layers.
- the multilayered approach may provide better long term stability by providing a sacrificial fracture layer which absorbs expansion mismatches during thermal cycling and long term operation.
- the interfaces between the fine layers and the fuel cell and interconnect respectively remain intact while physical stresses are absorbed by the central stress relief layer.
- a scanning electron micrograph demonstrates such a fracture in an autopsied fuel cell. The inventors have found that electrical conductivity through the contact material is maintained while the layers are compressed in a stack despite such horizontal fractures in the stress relief layer.
- the fracturing of the stress relief layer, or the interface between the stress relief layer and a fine outer layer may be facilitated by the addition of pore forming material or a fracture layer. This may be desirable or necessary if the cathode contact material is not pre-fired.
- a pore former may be added to the stress relief layer which will have the effect of weakening the stress relief layer internally, facilitating the formation of fractures.
- Pore formers may comprise organic particulate matter and may include graphite, corn starch or polystyrene, or other materials which combust at or about 500° C. The pore former burns out before reaching the operating temperature of the fuel cell, or during a pre-sintering process, introducing voids in the structure of the stress relief layer.
- the pore forming particles may preferably be about 1 ⁇ m to about 50 ⁇ m in size, and more preferably less than about 20 ⁇ m.
- the pore forming particles may be added to the coarse particle composition which is screen printed or otherwise applied to a fine particle layer. Sufficient pore forming material may be added to a level of about 20 to about 60 % by volume. With the addition of the pore former, the stress relief layer may be about 30-70% porous, preferably greater than about 50% porous, after combustion of the pore forming material. With larger pore forming particle sizes, the void spaces would of course be larger, but fewer in number.
- a weakened area may be introduced to the contact material by adding a fracture layer between the stress relief layer and the fine particle outer layer, or within the stress relief layer itself.
- the fracture layer may be added, for example, by adding a thin layer of an organic substance, which may the same as the pore forming substances described above. Suitable fracture layers may therefore comprise graphite, corn starch or polystyrene. Again, prior to reaching the operating temperature of the cell, or during a pre-sintering process, the fracture layer will burn out, leaving a weakened fracture plane.
- the fracture layer may be applied by spraying a suspension of the particles or by screen printing. Preferably, the fracture layer may be about 1-20 ⁇ m thick.
- a pre-fractured stress relief layer may be provided.
- a fine layer and a coarse stress relief layer may be applied to each of the cathode and the interconnect and allowed to dry.
- the coarse layer may or may not include pore formers as described above.
- the respective stress relief layers are pressed together.
- the boundary between the two coarse stress relief layers forms a fracture plane, creating what is in effect a single pre-fractured stress relief layer.
- the two coarse stress relief layers may include pore forming particles as described above.
- a pre-fractured stress layer may be formed by pressing together a fracture layer formed from a layer of a pore forming material as described above and a coarse layer.
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- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/904,563 US7190568B2 (en) | 2004-11-16 | 2004-11-16 | Electrically conductive fuel cell contact materials |
PCT/CA2005/001695 WO2006053422A1 (en) | 2004-11-16 | 2005-11-04 | Electrically conductive fuel cell contact materials |
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EP1825553A1 EP1825553A1 (en) | 2007-08-29 |
EP1825553A4 EP1825553A4 (en) | 2012-01-11 |
EP1825553B1 true EP1825553B1 (en) | 2018-12-26 |
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EP05803472.9A Active EP1825553B1 (en) | 2004-11-16 | 2005-11-04 | Electrically conductive fuel cell contact materials |
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US (1) | US7190568B2 (ja) |
EP (1) | EP1825553B1 (ja) |
JP (1) | JP5279272B2 (ja) |
AU (1) | AU2005306525B2 (ja) |
CA (1) | CA2588025C (ja) |
DK (1) | DK1825553T3 (ja) |
WO (1) | WO2006053422A1 (ja) |
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EP1850412A1 (en) * | 2006-04-26 | 2007-10-31 | Technical University of Denmark | A multi-layer coating |
GB0715225D0 (en) | 2007-08-03 | 2007-09-12 | Rolls Royce Fuel Cell Systems | A fuel cell and a method of manufacturing a fuel cell |
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CN102217130A (zh) * | 2008-11-21 | 2011-10-12 | 博隆能源股份有限公司 | 用于生产燃料电池组件的涂覆工艺 |
JP5388833B2 (ja) * | 2009-12-24 | 2014-01-15 | 京セラ株式会社 | セルスタックおよびそれを具備する燃料電池モジュールならびに燃料電池装置 |
KR101300157B1 (ko) | 2009-12-28 | 2013-08-26 | 주식회사 포스코 | 고체 산화물 연료 전지용 복합 세라믹 접촉재 및 그 제조방법 |
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2004
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-
2005
- 2005-11-04 DK DK05803472.9T patent/DK1825553T3/en active
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- 2005-11-04 EP EP05803472.9A patent/EP1825553B1/en active Active
- 2005-11-04 WO PCT/CA2005/001695 patent/WO2006053422A1/en active Application Filing
- 2005-11-04 AU AU2005306525A patent/AU2005306525B2/en not_active Ceased
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Title |
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Also Published As
Publication number | Publication date |
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EP1825553A4 (en) | 2012-01-11 |
JP2008521179A (ja) | 2008-06-19 |
JP5279272B2 (ja) | 2013-09-04 |
US7190568B2 (en) | 2007-03-13 |
US20060104008A1 (en) | 2006-05-18 |
DK1825553T3 (en) | 2019-02-18 |
AU2005306525B2 (en) | 2010-07-15 |
CA2588025C (en) | 2013-07-30 |
CA2588025A1 (en) | 2006-05-26 |
EP1825553A1 (en) | 2007-08-29 |
WO2006053422A1 (en) | 2006-05-26 |
AU2005306525A1 (en) | 2006-05-26 |
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